Basecoat acid neutralization through inorganic salts

ABSTRACT

The present invention provides a system comprising an allophanate composition comprising a neutralized polyol, a polyuretdione resin, a tertiary amine catalyst, an additive package, and a reducer; and a neutralized basecoat comprising an inorganic salt and a pigment. The present invention further provides a method of making an allophanate system comprising combining a neutralized polyol with a polyuretdione resin in the presence of a tertiary amine catalyst, an additive package, and a reducer to produce an allophanate composition, and contacting the allophanate composition with a neutralized basecoat comprising an inorganic salt and a pigment. The system may be used to make coatings, adhesives, castings, composites, and sealants in which clear-coating on neutralized pigmented basecoats is much improved in comparison to coating on non-neutralized basecoats.

FIELD OF THE INVENTION

The present invention relates, in general to polymers, and morespecifically, to polymers made with neutralized polyols, uretdiones andtertiary amine catalysts that cure over neutralized basecoats. Theresulting allophanate polymers may be used to make coatings, adhesives,castings, composites, and sealants.

BACKGROUND OF THE INVENTION

Polyurethane-forming compositions are widely used in a variety ofcommercial, industrial and household applications, such as in automotiveclear-coat and seat cushion applications. Polyurethane systems thatemploy isocyanates which are pre-reacted with monofunctional reagents toform relatively thermally labile compounds are called blockedisocyanates. Uretdiones are a type of blocked isocyanate. Uretdiones aretypically prepared by dimerizing an isocyanate to form uretdione(s) withunreacted isocyanate end-groups which can then be extended with a polyolto form a polymeric material containing two or more uretdione groups inthe polymer chain. In some literature, uretdiones are referred to as“1,3-diaza-2,4-cyclobutanones”, “1,3-diazatidin-2,4-diones”,“2,4-dioxo-1,3-diazetidines”, “urethdiones” or “uretidiones”. Typically,the polymer has few, if any, free isocyanate groups, which is achievedby controlling the stoichiometry of the polyisocyanate, of the polyol,and by the use of a blocking agent.

The reaction of uretdiones with polyols to form polyurethane coatings iswell known in the art, especially in polyurethane powder coatings.However, the creation of allophanates from uretdiones and polyols atambient or low temperatures in the presence of a tertiary amine catalysthas not been well-studied in the literature. To the best of the presentinventors' knowledge, no one has developed a cross-linking approachusing neutralized polyols to promote successful conversion of uretdioneto allophanate at ambient or low temperatures in the presence oftertiary amine catalysts over neutralized basecoats.

SUMMARY OF THE INVENTION

Uretdione-based clear coats face some challenges when applied overpigmented basecoats due to the acidic nature of the basecoats. Whenbasecoats are neutralized with an inorganic salt, uretdione-basedclear-coating is much improved in comparison to non-neutralizedbasecoats.

Accordingly, the present invention attempts to alleviate problemsinherent in the art by providing such an alternative cross-linkingapproach to obtain compositions having physical properties similar tothose of polyurethane compositions. To increase the conversion rate ofuretdione and polyol to form allophanate groups at ambient or lowtemperatures in the presence of a tertiary amine catalyst over aneutralized basecoat, the acidity of the polyol, and basecoat, and moregenerally, the acidity of the system is minimized or eliminated. Thus,various embodiments of the inventive approach involve crosslinkingpolyuretdione resins with neutralized polyols in the presence of atertiary amine catalyst over a neutralized basecoat. The polyol may beneutralized by reaction with an epoxy or cabodiimide at a temperatureranging from room temperature (21° C.-24° C.) to 1200. The resultingallophanate polymer may be used to make coatings, adhesives, castings,composites, and sealants. The basecoat may be neutralized by complexformation with an inorganic salt. The uretdione-based clear-coating ofthe invention may be applied over neutralized basecoats.

It is understood that the invention disclosed and described in thisspecification is not limited to the embodiments summarized in thisSummary.

DETAILED DESCRIPTION OF THE INVENTION

The present invention will now be described for purposes of illustrationand not limitation. Except in the operating examples, or where otherwiseindicated, all numbers expressing quantities, percentages, and so forthin the specification are to be understood as being modified in allinstances by the term “about.”

Any numerical range recited in this specification is intended to includeall sub-ranges of the same numerical precision subsumed within therecited range. For example, a range of “1.0 to 10.0” is intended toinclude all sub-ranges between (and including) the recited minimum valueof 1.0 and the recited maximum value of 10.0, that is, having a minimumvalue equal to or greater than 1.0 and a maximum value equal to or lessthan 10.0, such as, for example, 2.4 to 7.6. Any maximum numericallimitation recited in this specification is intended to include alllower numerical limitations subsumed therein and any minimum numericallimitation recited in this specification is intended to include allhigher numerical limitations subsumed therein. Accordingly, Applicantreserves the right to amend this specification, including the claims, toexpressly recite any sub-range subsumed within the ranges expresslyrecited herein. All such ranges are intended to be inherently describedin this specification such that amending to expressly recite any suchsub-ranges would comply with the requirements of 35 U.S.C. § 112(a), and35 U.S.C. § 132(a).

Any patent, publication, or other disclosure material identified hereinis incorporated by reference into this specification in its entiretyunless otherwise indicated, but only to the extent that the incorporatedmaterial does not conflict with existing definitions, statements, orother disclosure material expressly set forth in this specification. Assuch, and to the extent necessary, the express disclosure as set forthin this specification supersedes any conflicting material incorporatedby reference herein. Any material, or portion thereof, that is said tobe incorporated by reference into this specification, but whichconflicts with existing definitions, statements, or other disclosurematerial set forth herein, is only incorporated to the extent that noconflict arises between that incorporated material and the existingdisclosure material. Applicant reserves the right to amend thisspecification to expressly recite any subject matter, or portionthereof, incorporated by reference herein.

Reference throughout this specification to “various non-limitingembodiments,” “certain embodiments,” or the like, means that aparticular feature or characteristic may be included in an embodiment.Thus, use of the phrase “in various non-limiting embodiments,” “incertain embodiments,” or the like, in this specification does notnecessarily refer to a common embodiment, and may refer to differentembodiments. Further, the particular features or characteristics may becombined in any suitable manner in one or more embodiments. Thus, theparticular features or characteristics illustrated or described inconnection with various or certain embodiments may be combined, in wholeor in part, with the features or characteristics of one or more otherembodiments without limitation. Such modifications and variations areintended to be included within the scope of the present specification.

The grammatical articles “a”, “an”, and “the”, as used herein, areintended to include “at least one” or “one or more”, unless otherwiseindicated, even if “at least one” or “one or more” is expressly used incertain instances. Thus, these articles are used in this specificationto refer to one or more than one (i.e., to “at least one”) of thegrammatical objects of the article. By way of example, and withoutlimitation, “a component” means one or more components, and thus,possibly, more than one component is contemplated and may be employed orused in an implementation of the described embodiments. Further, the useof a singular noun includes the plural, and the use of a plural nounincludes the singular, unless the context of the usage requiresotherwise.

In various embodiments, the present invention provides a systemcomprising an allophanate composition comprising a neutralized polyol, apolyuretdione resin, a tertiary amine catalyst, an additive package, anda reducer; and a neutralized basecoat comprising an inorganic salt and apigment. In certain embodiments, the present invention further providesa method of making an allophanate system comprising combining aneutralized polyol with a polyuretdione resin in the presence of atertiary amine catalyst, an additive package, and a reducer to producean allophanate composition, and contacting the allophanate compositionwith a neutralized basecoat comprising an inorganic salt and a pigment.The polyol may be neutralized with a carbodiimide or an epoxy acidscavenger at a temperature ranging from room temperature (21° C.-24° C.)to 120° C. The basecoat may be neutralized with an inorganic saltthrough complex formation with acidic groups within the basecoat. Thus,the present invention provides a method for producing an allophanatepolymer over neutralized basecoats by the following route:

The inventive allophanate polymer system is particularly applicable inproducing coatings, adhesives, castings, composites, and sealants.

As used herein, the term “polymer” encompasses prepolymers, oligomersand both homopolymers and copolymers; the prefix “poly” in this contextreferring to two or more. As used herein, the term “molecular weight”,when used in reference to a polymer, refers to the number averagemolecular weight, unless otherwise specified.

As used herein, the term “polyol” refers to compounds comprising atleast two free hydroxy groups. Polyols include polymers comprisingpendant and terminal hydroxy groups.

As used herein, the term “coating composition” refers to a mixture ofchemical components that will cure and form a coating when applied to asubstrate.

The terms “adhesive” or “adhesive compound”, refer to any substance thatcan adhere or bond two items together. Implicit in the definition of an“adhesive composition” or “adhesive formulation” is the concept that thecomposition or formulation is a combination or mixture of more than onespecies, component or compound, which can include adhesive monomers,oligomers, and polymers along with other materials.

A “sealant composition” refers to a composition which may be applied toone or more surfaces to form a protective barrier, for example, toprevent ingress or egress of solid, liquid or gaseous material oralternatively to allow selective permeability through the barrier to gasand liquid. In particular, it may provide a seal between surfaces.

A “casting composition” refers to a mixture of liquid chemicalcomponents which is usually poured into a mold containing a hollowcavity of the desired shape, and then allowed to solidify.

A “composite” refers to a material made from two or more polymers,optionally containing other kinds of materials. A composite hasdifferent properties from those of the individual polymers/materialswhich make it up.

“Cured,” “cured composition” or “cured compound” refers to componentsand mixtures obtained from reactive curable original compound(s) ormixture(s) thereof which have undergone chemical and/or physical changessuch that the original compound(s) or mixture(s) is(are) transformedinto a solid, substantially non-flowing material. A typical curingprocess may involve crosslinking.

The term “curable” means that an original compound(s) or compositionmaterial(s) can be transformed into a solid, substantially non-flowingmaterial by means of chemical reaction, crosslinking, radiationcrosslinking, or the like. Thus, compositions of the invention arecurable, but unless otherwise specified, the original compound(s) orcomposition material(s) is(are) not cured.

The term “basecoat” means the first (undermost) layer applied to thesurface of a substrate prior to application of a subsequent or finishingcoat. The term encompasses basecoats, undercoats, and tiecoats.

The components useful in the present invention comprise apolyisocyanate. As used herein, the term “polyisocyanate” refers tocompounds comprising at least two unreacted isocyanate groups, such asthree or more unreacted isocyanate groups. The polyisocyanate maycomprise diisocyanates such as linear aliphatic polyisocyanates,aromatic polyisocyanates, cycloaliphatic polyisocyanates and aralkylpolyisocyanates.

Particularly preferred in the present invention are those blockedisocyanates known as uretdiones. The uretdiones useful in the inventionmay be obtained by catalytic dimerization of polyisocyanates by methodswhich are known to those skilled in the art. Examples of dimerizationcatalysts include, but are not limited to, trialkylphosphines,aminophosphines and aminopyradines such as dimethylaminopyridines, andtris(dimethylamino)phosphine, as well as any other dimerizationcatalyst. The result of the dimerization reaction depends, in a mannerknown to the skilled person, on the catalyst used, on the processconditions and on the polyisocyanates employed. In particular, it ispossible for products to be formed which contain on average more thanone uretdione group per molecule, the number of uretdione groups beingsubject to a distribution. The (poly)uretdiones may optionally containisocyanurate, biuret, allophanate, and iminooxadiazine dione groups inaddition to the uretdione groups.

The uretdiones are NCO-functional compounds and may be subjected to afurther reaction, for example, blocking of the free NCO groups orfurther reaction of NCO groups with NCO-reactive compounds having afunctionality of two or more to extend the uretdiones to formpolyuretdione prepolymers. This gives compounds containing uretdionegroups and of higher molecular weight, which, depending on the chosenproportions, may also contain NCO groups, be free of NCO groups or maycontain isocyanate groups that are blocked.

Suitable blocking agents include, but are not limited to, alcohols,lactams, oximes, malonates, alkyl acetoacetates, triazoles, phenols,imidazoles, pyrazoles and amines, such as butanone oxime,diisopropylamine, 1,2,4-triazole, dimethyl-1,2,4-triazole, imidazole,diethyl malonate, ethyl acetoacetate, acetone oxime,3,5-dimethylpyrazole, caprolactam, N-tert-butylbenzylamine andcyclopentanone including mixtures of these blocking agents.

Examples of NCO-reactive compounds with a functionality of two or moreinclude polyols. In some embodiments, the NCO-reactive compounds areused in amounts sufficient to react with all free NCO groups in theuretdione. By “free NCO groups” it is meant all NCO groups not presentas part of the uretdione, isocyanurate, biuret, allophanate andiminooxadiazine dione groups.

The resulting polyuretdione contains at least 2, such as from 2 to 10uretdione groups. More preferably, the polyuretdione contains from 5% to45% uretdione, 10% to 55% urethane, and less than 2% isocyanate groups.The percentages are by weight based on total weight of resin containinguretdione, urethane, and isocyanate.

Suitable polyisocyanates for producing the uretdiones useful inembodiments of the invention include, organic diisocyanates representedby the formula

R(NCO)₂

wherein R represents an organic group obtained by removing theisocyanate groups from an organic diisocyanate having(cyclo)aliphatically bound isocyanate groups and a molecular weight of112 to 1000, preferably 140 to 400. Preferred diisocyanates for theinvention are those represented by the formula wherein R represents adivalent aliphatic hydrocarbon group having from 4 to 18 carbon atoms, adivalent cycloaliphatic hydrocarbon group having from 5 to 15 carbonatoms, or a divalent araliphatic hydrocarbon group having from 7 to 15carbon atoms.

Examples of the organic diisocyanates which are particularly suitablefor the present invention include 1,4-tetramethylene diisocyanate,1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylenediisocyanate, 1,12-dodecamethylene diisocyanate, cyclohexane-1,3- and1,4-diisocyanate, 1-isocyanato-2-isocyanato-methyl cyclopentane,1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl cyclohexane (isophoronediisocyanate or IPDI), bis-(4-isocyanatocyclohexyl)methane, 1,3- and1,4-bis(isocyanatomethyl)-cyclohexane,bis-(4-isocyanato-3-methyl-cyclohexyl)-methane,α,α,α′,α′-tetramethyl-1,3- and 1,4-xylene diisocyanate,1-isocyanato-1-methyl-4(3)-isocyanato-methyl cyclohexane, and 2,4- and2,6-hexahydrotoluene diisocyanate, toluene diisocyanate (TDI),diphenylmethane diisocyanate (MDI), pentane diisocyanate(PDI)—bio-based), and, isomers of any of these; or combinations of anyof these. Mixtures of diisocyanates may also be used. Preferreddiisocyanates include 1,6-hexamethylene diisocyanate, isophoronediisocyanate, and bis(4-isocyanatocyclohexyl)-methane because they arereadily available and yield relatively low viscosity polyuretdionepolyurethane oligomers.

In some embodiments, the uretdiones may comprise from 35% to 85% resinsolids in the composition of present invention, excluding solvents,additives or pigments (colorants). In other embodiments, from 50% to 85%and in still other embodiments, 60% to 85%. The uretdiones may compriseany resin solids amount ranging between any combinations of thesevalues, inclusive of the recited values.

In various embodiments of the present invention, the reaction mixturecontaining the polyuretdione and the neutralized polyol in the presenceof a tertiary amine catalyst may be heated to a temperature of 140° C.,in other embodiments to a temperature of from 20° C. to 140° C.

The polyols useful in the present invention may be either low molecularweight (62-399 Da, as determined by gel permeation chromatography) orhigh molecular weight (400 to 10,000 Da, as determined by gel permeationchromatography) materials and in various embodiments will have averagehydroxyl values as determined by ASTM E222-10, Method B, of between 1000and 10, and preferably between 500 and 50.

The polyols in the present invention include low molecular weight diols,triols and higher alcohols and polymeric polyols such as polyesterpolyols, polyether polyols, polycarbonate polyols, polyurethane polyolsand hydroxy-containing (meth)acrylic polymers.

The low molecular weight diols, triols and higher alcohols useful in theinstant invention are known to those skilled in the art. In manyembodiments, they are monomeric and have hydroxy values of 200 andabove, usually within the range of 1500 to 200. Such materials includealiphatic polyols, particularly alkylene polyols containing from 2 to 18carbon atoms. Examples include ethylene glycol, 1,4-butanediol,1,6-hexanediol; cycloaliphatic polyols such as cyclohexane dimethanol.Examples of triols and higher alcohols include trimethylol propane andpentaerythritol. Also useful are polyols containing ether linkages suchas diethylene glycol and triethylene glycol.

In various embodiments, the suitable polyols are polymeric polyolshaving hydroxyl values less than 200, such as 10 to 180. Examples ofpolymeric polyols include polyalkylene ether polyols, polyester polyolsincluding hydroxyl-containing polycaprolactones, hydroxy-containing(meth)acrylic polymers, polycarbonate polyols and polyurethane polymers.

Examples of polyether polyols include poly(oxytetramethylene) glycols,poly(oxyethylene) glycols, and the reaction product of ethylene glycolwith a mixture of propylene oxide and ethylene oxide.

Also useful are polyether polyols formed from the oxyalkylation ofvarious polyols, for example, glycols such as ethylene glycol,1,4-butane glycol, 1,6-hexanediol, and the like, or higher polyols, suchas trimethylol propane, pentaerythritol and the like. One commonlyutilized oxyalkylation method is by reacting a polyol with an alkyleneoxide, for example, ethylene oxide in the presence of an acidic or basiccatalyst.

Polyester polyols can also be used as a polymeric polyol component inthe certain embodiments of the invention. The polyester polyols can beprepared by the polyesterification of organic polycarboxylic acids oranhydrides thereof with organic polyols. Preferably, the polycarboxylicacids and polyols are aliphatic or aromatic dibasic acids and diols.

The diols which may be employed in making the polyester include alkyleneglycols, such as ethylene glycol and butylene glycol, neopentyl glycoland other glycols such as cyclohexane dimethanol, caprolactone diol (forexample, the reaction product of caprolactone and ethylene glycol),polyether glycols, for example, poly(oxytetramethylene) glycol and thelike. However, other diols of various types and, as indicated, polyolsof higher functionality may also be utilized in various embodiments ofthe invention. Such higher polyols can include, for example, trimethylolpropane, trimethylol ethane, pentaerythritol, and the like, as well ashigher molecular weight polyols such as those produced by oxyalkylatinglow molecular weight polyols. An example of such high molecular weightpolyol is the reaction product of 20 moles of ethylene oxide per mole oftrimethylol propane.

The acid component of the polyester consists primarily of monomericcarboxylic acids or anhydrides having 2 to 18 carbon atoms per molecule.Among the acids which are useful are phthalic acid, isophthalic acid,terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid,adipic acid, azelaic acid, sebacic acid, maleic acid, glutaric acid,chlorendic acid, tetrachlorophthalic acid and other dicarboxylic acidsof varying types. Also, there may be employed higher polycarboxylicacids such as trimellitic acid and tricarballylic acid (where acids arereferred to above, it is understood that the anhydrides of those acidswhich form anhydrides can be used in place of the acid). Also, loweralkyl esters of acids such as dimethyl glutamate can be used.

In addition to polyester polyols formed from polybasic acids andpolyols, polycaprolactone-type polyesters can also be employed. Theseproducts are formed from the reaction of a cyclic lactone such asε-caprolactone with a polyol with primary hydroxyls such as thosementioned above. Such products are described in U.S. Pat. No. 3,169,949.

In addition to the polyether and polyester polyols, hydroxy-containing(meth)acrylic polymers or (meth)acrylic polyols can be used as thepolyol component.

Among the (meth)acrylic polymers are polymers of 2 to 20 percent byweight primary hydroxy-containing vinyl monomers such as hydroxyalkylacrylate and methacrylate having 2 to 6 carbon atoms in the alkyl groupand 80 to 98 percent by weight of other ethylenically unsaturatedcopolymerizable materials such as alkyl(meth)acrylates; the percentagesby weight being based on the total weight of the monomeric charge.

Examples of suitable hydroxy alkyl(meth)acrylates are hydroxy ethyl andhydroxy butyl(meth)acrylate. Examples of suitable alkyl acrylates and(meth)acrylates are lauryl methacrylate, 2-ethylhexyl methacrylate andn-butyl acrylate (n-BA).

In addition to the acrylates and methacrylates, other copolymerizablemonomers which can be copolymerized with the hydroxyalkyl(meth)acrylates include ethylenically unsaturated materials such asmonoolefinic and diolefinic hydrocarbons, halogenated monoolefinic anddiolefinic hydrocarbons, unsaturated esters of organic and inorganicacids, amides and esters of unsaturated acids, nitriles and unsaturatedacids and the like. Examples of such monomers include styrene,1,3-butadiene, acrylamide, acrylonitrile, α-methyl styrene, α-methylchlorostyrene, vinyl butyrate, vinyl acetate, alkyl chloride, divinylbenzene, diallyl itaconate, triallyl cyanurate and mixtures thereof.Preferably, these other ethylenically unsaturated materials are used inadmixture with the above-mentioned acrylates and methacrylates.

In certain embodiments of the invention, the polyol may be apolyurethane polyol. These polyols can be prepared by reacting any ofthe above-mentioned polyols with a minor amount of polyisocyanate(OH/NCO equivalent ratio greater than 1:1) so that free primary hydroxylgroups are present in the product. In addition to the high molecularweight polyols mentioned above, mixtures of both high molecular weightand low molecular weight polyols such as those mentioned above may beused.

Suitable hydroxy-functional polycarbonate polyols may be those preparedby reacting monomeric diols (such as 1,4-butanediol, 1,6-hexanediol,di-, tri- or tetraethylene glycol, di-, tri- or tetrapropylene glycol,3-methyl-1,5-pentanediol, 4,4′-dimethylolcyclohexane and mixturesthereof) with diaryl carbonates (such as diphenyl carbonate, dialkylcarbonates (such as dimethyl carbonate and diethyl carbonate), alkylenecarbonates (such as ethylene carbonate or propylene carbonate), orphosgene. Optionally, a minor amount of higher functional, monomericpolyols, such as trimethylolpropane, glycerol or pentaerythritol, may beused.

In various embodiments of the invention, the polyol is neutralized, forexample by the addition of an epoxy or carbodiimide acid scavenger andthe basecoat by the addition of an inorganic salt. The present inventorsbelieve, without wishing to be bound to any specific theory, that theseacid scavengers covalently bind to carboxylic and acrylic acid groupswithin the polyols and the basecoat, respectively.

Suitable epoxy or carbodiimide acid scavenging compounds arecommercially available from a variety of suppliers such as, for example,the monomeric carbodiimides sold under the STABAXOL trade name fromRhein Chemie, and bis-(2,6-diisopropylphenyl) carbodiimide sold asEUSTAB HS-700 by Eutec Chemical Co., Ltd. Glycidyl ethers, such as1,4-cyclohexanedimethanol diglycidyl ether, commercially available fromAir Products as EPODIL 757 are also suitable in the practice of thepresent invention.

Inorganic salts should be complexed with the acidic groups within thebasecoat. The present inventors believe, without wishing to be bound toany specific theory, that these inorganic salts act as acid scavengersby complexing with the carboxylic and acrylic acid groups within thebasecoat. A preferred type of inorganic salt for use in variousembodiments of the present invention contains a metal ion. Examples ofsuitable metal ions for inclusion in the inorganic salts include, butare not limited to, titanium, vanadium, aluminum chromium, manganese,potassium, iron, cobalt, nickel, lithium, copper, zirconium, zinc, andthe lanthanides (lanthanum, cerium, praseodymium, neodymium, promethium,samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium,thulium, ytterbium, and lutetium). Suitable inorganic salts for use inthe present invention include, but are not limited to, metalacetylacetonates such as zinc(II) acetylacetonate, aluminumacetylacetonate, iron(III) acetylacetonate, lithium acetylacetonate,nickel(II) acetylacetonate, zirconium(IV) acetylacetonate, and potassiumacetylacetonate.

In various embodiments, the neutralization of the polyol and of thebasecoat is conducted at any temperature ranging from room temperature(21° C.-24° C.) to 120° C., in other embodiments from room temperature(21° C.-24° C.) to 80° C. and in certain embodiments at room temperature(21° C.-24° C.).

Examples of suitable solvents include, but are not limited to aliphaticand aromatic hydrocarbons such as toluene, xylene, isooctane, acetone,butanone, methyl ethyl ketone, methyl amyl ketone, methyl isobutylketone, ethyl acetate, butyl acetate, pentyl acetate, tetrahydrofuran,ethyl ethoxypropionate, N-methyl-pyrrolidone, dimethylacetamide anddimethylformamide solvent naphtha, SOLVESSO 100 or HYDROSOL (ARAL),ethers, or mixtures thereof.

Urethane reducers are available in slow, medium and fast formulations,and may improve atomization, flow and leveling, which provide a smoothfinish with less “orange peel.” Depending on the “speed” of the reducer,it may contain various combinations of compounds including, but notlimited to, n-butyl acetate, ethyl acetate, 2-methoxy-1-methylethylacetate, 1-methoxy-2-propyl acetate, 2-methoxy-1-propyl-acetate,2-ethoxyethyl acetate, n-heptane, methylcyclohexane, toluene, acetone,Varnish Makers and Painter (VM&P) naphtha, naphtha, light aliphaticsolvent naphtha, acetate, isobutyl acetate, mixed xylenes, ethylbenzene,methyl ethyl ketone, dimethyl ketone, methyl n-amyl ketone, methylisobutyl ketone, 1,2,4-trimethyl benzene, isopropylbenzene, ethylbenzene, 1-chloro-4-(triflouromethyl) benzene, propylene glycol methylether, and ethyl-3-ethoxy propionate.

In various embodiments, the basecoats useful in the invention includeone or more colorants, such as pigments and dyes. Any suitable pigmentcan be used in the basecoat of the present invention. Examples ofsuitable pigments include inorganic white pigments, inorganic chromaticpigments, iron oxide pigments, oxidic mixed-phase pigments, organicpigments, and inorganic black pigments.

As inorganic white pigments, mention should be made in particular ofoxides, such as titanium dioxide, zinc oxide (ZnO, zinc white),zirconium oxide, carbonates such as lead white, sulfates, such as leadsulfate, and sulfides such as zinc sulfide, and lithopones; titaniumdioxide is particularly preferred.

As inorganic chromatic pigments, mention should be made of those fromthe group of oxides and hydroxides in the form of their individualinorganic compounds or mixed phases, especially iron oxide pigments,chromium oxide pigments and oxidic mixed-phase pigments with rutile orspinel structure, and also bismuth vanadate, cadmium, cerium sulfide,chromate, ultramarine and iron blue pigments.

Examples of iron oxide pigments are Color Index Pigment Yellow 42,Pigment Red 101, Pigment Blue 11, Pigment Brown 6, and transparent ironoxide pigments. Examples of chromium oxide pigments are Color IndexPigment Green 17 and Pigment Green 18.

Examples of oxidic mixed-phase pigments are nickel titanium yellow andchromium titanium yellow, cobalt green and cobalt blue, zinc iron brownand chromium iron brown, and also iron manganese black and spinel black.

Examples of preferred organic pigments are those of the monoazo, disazo,laked azo, β-naphthol, Naphiol AS, benzimidazolone, disazo condensation,azo metal complex, isoindoline and isoindolinone series, and alsopolycyclic pigments such as those from the phthalocyanine, quinacridone,perylene, perinone, thioindigo, anthraquinone, dioxazine, quinophthaloneand diketopyrrolopyrrole series. Also suitable are laked dyes such asCa, Mg and Al lakes of dyes containing sulfonic acid or carboxylic acidgroups, and also carbon blacks, which for the purposes of thisspecification are taken to be pigments and of which a large number areknown. Mention should be made in particular of acidic to alkaline carbonblacks obtained by the furnace black process, and also chemicallysurface-modified carbon blacks, examples being sulfo- orcarboxyl-containing carbon blacks.

Examples of inorganic black pigments that should be mentioned includethose as already described above together with the inorganic chromaticpigments, especially black iron oxide, spinel black, and black oxidicmixed-phase pigments.

The basecoat can contain the pigment at a level of at least 1%, in somecases at least 2%, in other cases at least 5% by weight, in somesituations at least 10% and in other situations at least 15% by weight.Also, the basecoat can contain the pigment at a level of up to 60%, insome cases up to 50%, in other cases up to 40%, in some situations up to35% and in other situations up to 30% by weight, based on the weight ofbasecoat. The amount of the pigment in the basecoat can be any of thevalues recited above or can range between any of the values recitedabove.

The composition of the invention may be contacted with the basecoat byany methods known to those skilled in the art, including but not limitedto, spraying, dipping, flow coating, rolling, brushing, pouring, and thelike. In certain embodiments, the inventive compositions may be appliedin the form of paints or lacquers onto any compatible substrate, suchas, for example, metals, plastics, ceramics, glass, and naturalmaterials. In various embodiments, the composition of the invention isapplied as a single layer. In other embodiments, the inventivecomposition may be applied as multiple layers as needed.

The compositions of the present invention (clear-coating, top-coat, andbasecoat) may further include any of a variety of additives such asdefoamers, devolatilizers, surfactants, thickeners, flow controladditives, colorants (including pigments and dyes) or surface additives.

The composition of the invention may be contacted with a substrate byany methods known to those skilled in the art, including but not limitedto, spraying, dipping, flow coating, rolling, brushing, pouring, and thelike. In some embodiments, the inventive compositions may be applied inthe form of paints or lacquers onto any compatible substrate, such as,for example, metals, plastics, ceramics, glass, and natural materials.In certain embodiments, the inventive composition is applied as a singlelayer. In other embodiments, the composition of the present inventionmay be applied as multiple layers as needed.

EXAMPLES

The non-limiting and non-exhaustive examples that follow are intended tofurther describe various non-limiting and non-exhaustive embodimentswithout restricting the scope of the embodiments described in thisspecification. All quantities given in “parts” and “percents” areunderstood to be by weight, unless otherwise indicated. Although thepresent invention is described in the instant Examples in the context ofa coating, those skilled in the art will appreciate it can also beequally applicable to adhesives, castings, composites, and sealants.

The following materials were used in preparing the compositions of theExamples:

-   BASECOAT A a black polyester refinish basecoat, commercially    available from BASF under DIAMONT product line;-   REDUCER A a universal medium reducer, commercially available from    BASF as RM UR 50, recommended for use in temperatures between    approximately 70° F.-85° F. (21.1° C.-29.4° C.);-   POLYOL A an aromatic free, branched hydroxyl-bearing polyester    polyol, commercially available from Covestro as DESMOPHEN 775 XP;-   ADDITIVE A an active anti-hydrolysis agent for polyester    polyurethanes, being used as an acid scavenger for acidic groups    within the polyols, commercially available from Rhein Chemie as    STABAXOL I;-   ADDITIVE B a surface additive on polyacrylate-basis for    solvent-borne coating systems and printing inks, commercially    available from BYK Chemie as BYK 358N;-   ADDITIVE C zinc(II) acetylacetonate, an inorganic salt (inorganic    scavenger for acidic groups), commercially available from Fisher    Scientific;-   ADDITIVE D aluminum acetylacetonate, an inorganic salt (inorganic    scavenger for acidic groups), commercially available from Fisher    Scientific;-   ADDITIVE E iron(III) acetylacetonate, an inorganic salt (inorganic    scavenger for acidic groups), commercially available from Sigma    Aldrich;-   ADDITIVE F lithium acetylacetonate, an inorganic salt (inorganic    scavenger for acidic groups), commercially available from Fisher    Scientific;-   ADDITIVE G magnesium acetylacetonate, an inorganic salt (inorganic    scavenger for acidic groups), commercially available from Fisher    Scientific;-   ADDITIVE H nickel(II) acetylacetonate, an inorganic salt (inorganic    scavenger for acidic groups), commercially available from Sigma    Aldrich;-   ADDITIVE I zirconium(IV) acetylacetonate, an inorganic salt    (inorganic scavenger for acidic groups), commercially available from    Fisher Scientific;-   ADDITIVE J potassium acetylacetonate, an inorganic salt (inorganic    scavenger for acidic groups), commercially available from Alfa    Aesar;-   CATALYST A 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), tertiary amine    catalyst, commercially available from Air Products as POLYCAT DBU;    and-   URETDIONE A an IPDI based uretdione prepolymer, proprietary product    of Covestro, having a uretdione equivalent weight of 1,276 and a    viscosity of 817 cPs in 50% butyl acetate.

The BASECOAT formulations A, B, C, D, E, F, G, and H in Table I wereprepared following the same procedure. Five parts of respective ADDITIVE(C, D, E, F, G, H, I, and J) was mixed in with 100 parts of BASECOAT Aand grinded using glass beads in a metal can by using a paint shaker.After grinding, 50 parts of REDUCER A and the resulting mixture wasmixed in a 200 mL plastic container using a FLACKTEK speed mixer for oneminute followed by application using a conventional HVLP spray. TheBASECOAT formulation I is a reference formulation that did not need tobe mixed with any of the ADDITIVES C, D, E, F, G, H, I, and J.

The clear-coat Formulations A, B, C, D, E, F, G, H, and I in Table Iwere prepared as follows. POLYOL A had been reacted with ADDITIVE Aprior to formulation. In a 200 mL plastic container 9.52 parts of thePOLYOL A and ADDITIVE A reaction mixture, 0.38 parts ADDITIVE C, 0.20parts CATALYST A, 25.17 parts n-butyl acetate, and 64.74 parts URETDIONEA were added. The resulting mixture was mixed using a FLACKTEK speedmixer for one minute followed by application using a conventional HVLPspray.

Iron phosphate treated ACT B952, 4″×12″ test panels were used. Thicknessof basecoat was 2 mils (50 μm) wet and thickness of the one componentcoating was 5 mils (125 μm) wet (2 mils (50 μm) dry). The resultingpanels were used to test for MEK double rubs.

MEK double rubs were measured according to ASTM D4752-10(2015). Resultsreported are an average of three readings for each formulation. One day(RT) is the test results of the coatings (basecoat, clear-coat) thatwere cured at room temperature for 1 day (no long term basecoat aging).One day (100° C.) is the test results of the coatings (basecoat,clear-coat) that were cured at 100° C. for 30 minutes and resting atroom temperature for 1 day before testing (no long term basecoat aging).6 weeks (RT) is the test results of the coatings that ADDITIVES C, D, E,F, G, H, I and J had been aged with BASECOAT A at room temperature for 6weeks. Then the coatings (basecoat, clear-coat) were cured at roomtemperature for one day followed by MEK DR testing (basecoat had beenaged for 6 weeks). 6 weeks (100° C.) is the test results of the coatingsthat ADDITIVES C, D, E, F, G, H, I and J had been aged with BASECOAT Aat room temperature for 6 weeks. Then the coatings (basecoat,clear-coat) were cured at 100° C. for 30 minutes and resting at roomtemperature for 1 day before testing (basecoat had been aged for 6weeks).

TABLE I A B C D E F G H I BASECOAT BASECOAT A (mL) 100 100 100 100 100100 100 100 100 ADDITIVE C 5 ADDITIVE D 5 ADDITIVE E 5 ADDITIVE F 5ADDITIVE G 5 ADDITIVE H 5 ADDITIVE I 5 ADDITIVE J 5 REDUCER A (mL) 50 5050 50 50 50 50 50 50 CLEAR-COAT POLYOL A 9.13 9.13 9.13 9.13 9.13 9.139.13 9.13 9.13 ADDITIVE A 0.39 0.39 0.39 0.39 0.39 0.39 0.39 0.39 0.39ADDITIVE C 0.38 0.38 0.38 0.38 0.38 0.38 0.38 0.38 0.38 CATALYST A 0.200.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 n-BA 25.17 25.17 25.17 25.1725.17 25.17 25.17 25.17 25.17 URETDIONE A 64.74 64.74 64.74 64.74 64.7464.74 64.74 64.74 64.74 MEK Double Rubs 1 Day (RT) 5 5 6 15 11 9 17 26 51 Day (100° C.) 43 17 12 34 47 21 56 78 5 6 Weeks (RT) 5 8 10 23 24 2017 33 5 6 Weeks (100° C.) 62 45 37 95 80 55 88 137 5

As can be appreciated by reference to Table I, Examples A, B, C, D, E,F, G, and H in Table I have some additive modification of the BASECOATA. Example I is a reference formulation that did not receive anyadditives into BASECOAT A. All examples A, B, C, D, E, F, G, H, and Ireceived the same clear-coat over basecoat. Looking at MEK double rubsresults, it is apparent to those skilled in the art that neutralizationof basecoat with the inorganic salt improves chemical resistance ofclear-coat significantly.

This specification has been written with reference to variousnon-limiting and non-exhaustive embodiments. However, it will berecognized by persons having ordinary skill in the art that varioussubstitutions, modifications, or combinations of any of the disclosedembodiments (or portions thereof) may be made within the scope of thisspecification. Thus, it is contemplated and understood that thisspecification supports additional embodiments not expressly set forthherein. Such embodiments may be obtained, for example, by combining,modifying, or reorganizing any of the disclosed steps, components,elements, features, aspects, characteristics, limitations, and the like,of the various non-limiting embodiments described in this specification.In this manner, Applicant reserves the right to amend the claims duringprosecution to add features as variously described in thisspecification, and such amendments comply with the requirements of 35U.S.C. § 112(a), and 35 U.S.C. § 132(a).

Various aspects of the subject matter described herein are set out inthe following numbered clauses:

1. A system comprising: an allophanate composition comprising aneutralized polyol, a polyuretdione resin, a tertiary amine catalyst, anadditive package, and a reducer, and a neutralized basecoat comprisingan inorganic salt and a pigment.

2. The system according to clause 1, wherein the tertiary amine is anamidine.

3. The system according to clause 1, wherein the tertiary amine isselected from the group consisting of one selected from the groupconsisting of 1,8-diazabicyclo[5.4.0]undec-7-ene,7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene,1,4,5,6-tetrahydro-1,2-dimethylpyrimidine, 1,2,4-triazole, sodiumderivative and 2-tert-butyl-1,1,3,3-tetramethylguanidine, andcombinations thereof.

4. The system according to one of clauses 1 to 3, wherein theneutralized polyol comprises the reaction product of a polyol and anacid scavenger selected from the group consisting of carbodiimides andepoxies.

5. The system according to clause 4, wherein the polyol is selected fromthe group consisting of polyalkylene ether polyols, polyester polyolshydroxyl containing polycaprolactones, hydroxyl-containing (meth)acrylicpolymers, polycarbonate polyols, polyurethane polyols, and combinationsthereof.

6. The system according to one of clauses 1 to 5, wherein theneutralized basecoat comprises the complexation product of a basecoatwith an inorganic salt.

7. The system according to clause 6, wherein the inorganic saltcomprises a metal.

8. The system according to clause 7, wherein the metal is selected fromthe group consisting of titanium, vanadium, aluminum chromium,manganese, potassium, iron, cobalt, nickel, lithium, copper, zirconium,zinc, lanthanum, cerium, praseodymium, neodymium, promethium, samarium,europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium,ytterbium, and lutetium.

9. The system according to clause 6, wherein the inorganic salt isselected from the group consisting of zinc(II) acetylacetonate, aluminumacetylacetonate, iron(III) acetylacetonate, lithium acetylacetonate,nickel(II) acetylacetonate, zirconium(IV) acetylacetonate, and potassiumacetylacetonate.

10. The system according to one of clauses 1 to 9, wherein the pigmentis selected from the group consisting of inorganic white pigments,inorganic chromatic pigments, iron oxide pigments, oxidic mixed-phasepigments, organic pigments, and inorganic black pigments.

11. The system according to one of clauses 1 to 10, wherein the pigmentis selected from the group consisting of titanium dioxide, zinc oxide(ZnO), zirconium oxide, lead white, lead sulfate, zinc sulfide, andlithopones, titanium dioxide, bismuth vanadate, cadmium, cerium sulfide,chromate, ultramarine iron blue pigments, Color Index Pigment Yellow 42,Pigment Red 101, Pigment Blue 11, Pigment Brown 6, transparent ironoxide pigments, Color Index Pigment Green 17, Pigment Green 18, nickeltitanium yellow, chromium titanium yellow, cobalt green, cobalt blue,zinc iron brown, chromium iron brown, iron manganese black, spinelblack, carbon black, and black iron oxide.

12. The system according to one of clauses 1 to 11, wherein the systemfurther includes an additive package selected from the group consistingof flow control additives, wetting agents, pigments (colorants), andsolvents.

13. The system according to one of clauses 1 to 12, wherein thepolyuretdione resin comprises the reaction product of catalyticdimerization of an isocyanate.

14. The system according to clause 13, wherein the isocyanate isselected from the group consisting of 1,4-tetramethylene diisocyanate,1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylenediisocyanate, 1,12-dodecamethylene diisocyanate, cyclohexane-1,3- and1,4-diisocyanate, 1-isocyanato-2-isocyanato-methyl cyclopentane,1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl cyclohexane (isophoronediisocyanate or IPDI), bis-(4-isocyanatocyclohexyl)methane, 1,3- and1,4-bis(isocyanatomethyl)-cyclohexane,bis-(4-isocyanato-3-methyl-cyclohexyl)-methane,α,α,α′,α′-tetramethyl-1,3- and 1,4-xylene diisocyanate,1-isocyanato-1-methyl-4(3)-isocyanato-methyl cyclohexane, and 2,4- and2,6-hexahydrotoluene diisocyanate, toluene diisocyanate (TDI),diphenylmethane diisocyanate (MDI), pentane diisocyanate(PDI)—bio-based, and, isomers of any of these.

15. The system according to one of clauses 1 to 14, wherein the reduceris selected from the group consisting of n-butyl acetate, ethyl acetate,2-methoxy-1-methylethyl acetate, 1-methoxy-2-propyl acetate,2-methoxy-1-propyl acetate, 2-ethoxyethyl acetate, n-heptane,methylcyclohexane, toluene, acetone, VM&P naphtha, naphtha, lightaliphatic solvent naphtha, acetate, isobutyl acetate, mixed xylenes,ethylbenzene, methyl ethyl ketone, dimethyl ketone, methyl n-amylketone, methyl isobutyl ketone, 1,2,4 trimethyl benzene,isopropylbenzene, ethyl benzene, 1-chloro-4 (triflouromethyl) benzene,propylene glycol methyl ether, and ethyl-3-ethoxy propionate andcombinations thereof.

16. One of a coating, an adhesive, a casting, a composite, and a sealantcomprising the system made according to one of clauses 1 to 15.

17. A method of applying the system according to one of clauses 1 to 16to a substrate, wherein the method comprises at least one of spraying,dipping, flow coating, rolling, brushing, and pouring.

18. A method of making an allophanate system comprising: combining aneutralized polyol with a polyuretdione resin in the presence of atertiary amine catalyst, an additive package, and a reducer to producean allophanate composition, and contacting the allophanate compositionwith a neutralized basecoat comprising an inorganic salt and a pigment.

19. The method according to clause 18 wherein the tertiary aminecatalyst comprises an amidine.

20. The method according to clause 18, wherein the tertiary amine isselected from the group consisting of one selected from the groupconsisting of 1,8-diazabicyclo[5.4.0]undec-7-ene,7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene,1,4,5,6-tetrahydro-1,2-dimethylpyrimidine, 1,2,4-triazole, sodiumderivative and 2-tert-butyl-1,1,3,3-tetramethylguanidine, andcombinations thereof.

21. The method according to one of clauses 18 to 20, wherein theneutralized polyol comprises the reaction product of a polyol and anacid scavenger selected from the group consisting of carbodiimides andepoxies.

22. The method according to clause 21, wherein the polyol is selectedfrom the group consisting of polyalkylene ether polyols, polyesterpolyols, hydroxyl containing polycaprolactones, hydroxyl-containing(meth)acrylic polymers, polycarbonate polyols, polyurethane polyols, andcombinations thereof.

23. The method according to one of clauses 18 to 22, wherein theneutralized basecoat comprises the complexation product of a basecoatwith an inorganic salt.

24. The system according to clause 23, wherein the inorganic saltcomprises a metal.

25. The system according to clause 24, wherein the metal is selectedfrom the group consisting of titanium, vanadium, aluminum chromium,manganese, potassium, iron, cobalt, nickel, lithium, copper, zirconium,zinc, lanthanum, cerium, praseodymium, neodymium, promethium, samarium,europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium,ytterbium, and lutetium.

26. The system according to clause 23, wherein the inorganic salt isselected from the group consisting of zinc(II) acetylacetonate, aluminumacetylacetonate, iron(III) acetylacetonate, lithium acetylacetonate,nickel(II) acetylacetonate, zirconium(IV) acetylacetonate, and potassiumacetylacetonate.

27. The method according to one of clauses 18 to 26, wherein the pigmentis selected from the group consisting of inorganic white pigments,inorganic chromatic pigments, iron oxide pigments, oxidic mixed-phasepigments, organic pigments, and inorganic black pigments.

28. The method according to one of clauses 18 to 27, wherein the pigmentis selected from the group consisting of titanium dioxide, zinc oxide(ZnO), zirconium oxide, lead white, lead sulfate, zinc sulfide, andlithopones, titanium dioxide, bismuth vanadate, cadmium, cerium sulfide,chromate, ultramarine iron blue pigments, Color Index Pigment Yellow 42,Pigment Red 101, Pigment Blue 11, Pigment Brown 6, transparent ironoxide pigments, Color Index Pigment Green 17, Pigment Green 18, nickeltitanium yellow, chromium titanium yellow, cobalt green, cobalt blue,zinc iron brown, chromium iron brown, iron manganese black, spinelblack, carbon black, and black iron oxide.

29. The method according to one of clauses 18 to 28, further includingan additive package selected from the group consisting of flow controladditives, wetting agents, pigments (colorants), and solvents.

30. The method according to one of clauses 18 to 29, wherein thepolyuretdione resin comprises the reaction product of catalyticdimerization of an isocyanate.

31. The method according to clause 30, wherein the isocyanate isselected from the group consisting of 1,4-tetramethylene diisocyanate,1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylenediisocyanate, 1,12-dodecamethylene diisocyanate, cyclohexane-1,3- and1,4-diisocyanate, 1-isocyanato-2-isocyanato-methyl cyclopentane,1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl cyclohexane (isophoronediisocyanate or IPDI), bis-(4-isocyanatocyclohexyl)methane, 1,3- and1,4-bis(isocyanatomethyl)-cyclohexane,bis-(4-isocyanato-3-methyl-cyclohexyl)-methane,α,α,α′,α′-tetramethyl-1,3- and 1,4-xylene diisocyanate,1-isocyanato-1-methyl-4(3)-isocyanato-methyl cyclohexane, and 2,4- and2,6-hexahydrotoluene diisocyanate, toluene diisocyanate (TDI),diphenylmethane diisocyanate (MDI), pentane diisocyanate(PDI)—bio-based, and, isomers of any of these.

32. The method according to one of clauses 18 to 31, wherein the reduceris selected from the group consisting of n-butyl acetate, ethyl acetate,2-methoxy-1-methylethyl acetate, 1-methoxy-2-propyl acetate,2-methoxy-1-propyl acetate, 2-ethoxyethyl acetate, n-heptane,methylcyclohexane, toluene, acetone, VM&P naphtha, naphtha, lightaliphatic solvent naphtha, acetate, isobutyl acetate, mixed xylenes,ethylbenzene, methyl ethyl ketone, dimethyl ketone, methyl n-amylketone, methyl isobutyl ketone, 1,2,4-trimethyl benzene,isopropylbenzene, ethyl benzene, 1-chloro-4 (triflouromethyl) benzene,propylene glycol methyl ether, and ethyl-3-ethoxy propionate andcombinations thereof.

33. One of a coating, an adhesive, a casting, a composite, and a sealantcomprising the allophanate system made according to one of clauses 18 to32.

34. A method of applying the allophanate system made according to one ofclauses 18 to 33 to a substrate, wherein the method comprises at leastone of spraying, dipping, flow coating, rolling, brushing, and pouring.

What is claimed is:
 1. A system comprising: an allophanate compositioncomprising, a neutralized polyol, a polyuretdione resin, a tertiaryamine catalyst, an additive package; and a neutralized basecoatcomprising, an inorganic salt, and a pigment.
 2. The system according toclaim 1, wherein the tertiary amine is an amidine.
 3. The systemaccording to claim 1, wherein the tertiary amine is selected from thegroup consisting of one selected from the group consisting of1,8-diazabicyclo[5.4.0]undec-7-ene,7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene,1,4,5,6-tetrahydro-1,2-dimethylpyrimidine, 1,2,4-triazole, sodiumderivative and 2-tert-butyl-1,1,3,3-tetramethylguanidine, andcombinations thereof.
 4. The system according to claim 1, wherein theneutralized polyol comprises the reaction product of a polyol and anacid scavenger selected from the group consisting of carbodiimides andepoxies.
 5. The system according to claim 4, wherein the polyol isselected from the group consisting of polyalkylene ether polyols,polyester polyols hydroxyl containing polycaprolactones,hydroxyl-containing (meth)acrylic polymers, polycarbonate polyols,polyurethane polyols, and combinations thereof.
 6. The system accordingto claim 1, wherein the neutralized basecoat comprises the reactionproduct of a basecoat with an inorganic salt.
 7. The system according toclaim 6, wherein the inorganic salt comprises a metal.
 8. The systemaccording to claim 7, wherein the metal is selected from the groupconsisting of titanium, vanadium, aluminum chromium, manganese,potassium, iron, cobalt, nickel, lithium, copper, zirconium, zinc,lanthanum, cerium, praseodymium, neodymium, promethium, samarium,europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium,ytterbium, and lutetium.
 9. The system according to claim 6, wherein theinorganic salt is selected from the group consisting of zinc(II)acetylacetonate, aluminum acetylacetonate, iron(III) acetylacetonate,lithium acetylacetonate, nickel(II) acetylacetonate, zirconium(IV)acetylacetonate, and potassium acetylacetonate.
 10. The system accordingto claim 1, wherein the pigment is selected from the group consisting ofinorganic white pigments, inorganic chromatic pigments, iron oxidepigments, oxidic mixed-phase pigments, organic pigments, and inorganicblack pigments.
 11. The system according to claim 1, wherein the pigmentis selected from the group consisting of titanium dioxide, zinc oxide(ZnO), zirconium oxide, lead white, lead sulfate, zinc sulfide, andlithopones, titanium dioxide, bismuth vanadate, cadmium, cerium sulfide,chromate, ultramarine iron blue pigments, Color Index Pigment Yellow 42,Pigment Red 101, Pigment Blue 11, Pigment Brown 6, transparent ironoxide pigments, Color Index Pigment Green 17, Pigment Green 18, nickeltitanium yellow, chromium titanium yellow, cobalt green, cobalt blue,zinc iron brown, chromium iron brown, iron manganese black, spinelblack, carbon black, and black iron oxide.
 12. The system according toclaim 1, wherein the system further includes an additive packageselected from the group consisting of flow control additives, wettingagents, pigments (colorants), and solvents.
 13. The system according toclaim 1, wherein the polyuretdione resin comprises the reaction productof catalytic dimerization of an isocyanate.
 14. The system according toclaim 13, wherein the isocyanate is selected from the group consistingof 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate,2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 1,12-dodecamethylenediisocyanate, cyclohexane-1,3- and 1,4-diisocyanate,1-isocyanato-2-isocyanato-methyl cyclopentane,1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl cyclohexane (isophoronediisocyanate or IPDI), bis-(4-isocyanatocyclohexyl)methane, 1,3- and1,4-bis(isocyanatomethyl)-cyclohexane,bis-(4-isocyanato-3-methyl-cyclohexyl)-methane,α,α,α′,α′-tetramethyl-1,3- and 1,4-xylene diisocyanate,1-isocyanato-1-methyl-4(3)-isocyanato-methyl cyclohexane, and 2,4- and2,6-hexahydrotoluene diisocyanate, toluene diisocyanate (TDI),diphenylmethane diisocyanate (MDI), pentane diisocyanate(PDI)—bio-based, and, isomers of any of these.
 15. The system accordingto claim 1, wherein the reducer is selected from the group consisting ofn-butyl acetate, ethyl acetate, 2-methoxy-1-methylethyl acetate,1-methoxy-2-propyl acetate, 2-methoxy-1-propyl acetate, 2-ethoxyethylacetate, n-heptane, methylcyclohexane, toluene, acetone, VM&P naphtha,naphtha, light aliphatic solvent naphtha, acetate, isobutyl acetate,mixed xylenes, ethylbenzene, methyl ethyl ketone, dimethyl ketone,methyl n-amyl ketone, methyl isobutyl ketone, 1,2,4 trimethyl benzene,isopropylbenzene, ethyl benzene, 1-chloro-4 (triflouromethyl) benzene,propylene glycol methyl ether, and ethyl-3-ethoxy propionate andcombinations thereof.
 16. One of a coating, an adhesive, a casting, acomposite, and a sealant comprising the system made according toclaim
 1. 17. A method of applying the system according to claim 1 to asubstrate, wherein the method comprises at least one of spraying,dipping, flow coating, rolling, brushing, and pouring.
 18. A method ofmaking an allophanate system comprising: combining a neutralized polyolwith a polyuretdione resin in the presence of a tertiary amine catalyst,an additive package, and a reducer to produce an allophanatecomposition; and contacting the allophanate composition with aneutralized basecoat comprising an inorganic salt and a pigment.
 19. Themethod according to claim 18 wherein the tertiary amine catalystcomprises an amidine.
 20. The method according to claim 18, wherein thetertiary amine is selected from the group consisting of one selectedfrom the group consisting of 1,8-diazabicyclo[5.4.0]undec-7-ene,7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene,1,4,5,6-tetrahydro-1,2-dimethylpyrimidine, 1,2,4-triazole, sodiumderivative and 2-tert-butyl-1,1,3,3-tetramethylguanidine, andcombinations thereof.
 21. The method according to claim 18, wherein theneutralized polyol comprises the reaction product of a polyol and anacid scavenger selected from the group consisting of carbodiimides andepoxies.
 22. The method according to claim 21, wherein the polyol isselected from the group consisting of polyalkylene ether polyols,polyester polyols, hydroxyl containing polycaprolactones,hydroxyl-containing (meth)acrylic polymers, polycarbonate polyols,polyurethane polyols, and combinations thereof.
 23. The method accordingto claim 18, wherein the neutralized basecoat comprises the reactionproduct of a basecoat with an inorganic salt.
 24. The system accordingto claim 23, wherein the inorganic salt comprises a metal.
 25. Thesystem according to claim 24, wherein the metal is selected from thegroup consisting of titanium, vanadium, aluminum chromium, manganese,potassium, iron, cobalt, nickel, lithium, copper, zirconium, zinc,lanthanum, cerium, praseodymium, neodymium, promethium, samarium,europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium,ytterbium, and lutetium.
 26. The system according to claim 23, whereinthe inorganic salt is selected from the group consisting of zinc(II)acetylacetonate, aluminum acetylacetonate, iron(III) acetylacetonate,lithium acetylacetonate, nickel(II) acetylacetonate, zirconium(IV)acetylacetonate, and potassium acetylacetonate.
 27. The method accordingto claim 18, wherein the pigment is selected from the group consistingof inorganic white pigments, inorganic chromatic pigments, iron oxidepigments, oxidic mixed-phase pigments, organic pigments, and inorganicblack pigments.
 28. The method according to claim 18, wherein thepigment is selected from the group consisting of titanium dioxide, zincoxide (ZnO), zirconium oxide, lead white, lead sulfate, zinc sulfide,and lithopones, titanium dioxide, bismuth vanadate, cadmium, ceriumsulfide, chromate, ultramarine iron blue pigments, Color Index PigmentYellow 42, Pigment Red 101, Pigment Blue 11, Pigment Brown 6,transparent iron oxide pigments, Color Index Pigment Green 17, PigmentGreen 18, nickel titanium yellow, chromium titanium yellow, cobaltgreen, cobalt blue, zinc iron brown, chromium iron brown, iron manganeseblack, spinel black, carbon black, and black iron oxide.
 29. The methodaccording to claim 18, further including an additive package selectedfrom the group consisting of flow control additives, wetting agents,pigments (colorants), and solvents.
 30. The method according to claim18, wherein the polyuretdione resin comprises the reaction product ofcatalytic dimerization of an isocyanate.
 31. The method according toclaim 30, wherein the isocyanate is selected from the group consistingof 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate,2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 1,12-dodecamethylenediisocyanate, cyclohexane-1,3- and 1,4-diisocyanate,1-isocyanato-2-isocyanato-methyl cyclopentane,1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl cyclohexane (isophoronediisocyanate or IPDI), bis-(4-isocyanatocyclohexyl)methane, 1,3- and1,4-bis(isocyanatomethyl)-cyclohexane,bis-(4-isocyanato-3-methyl-cyclohexyl)-methane,α,α,α′,α′-tetramethyl-1,3- and 1,4-xylene diisocyanate,1-isocyanato-1-methyl-4(3)-isocyanato-methyl cyclohexane, and 2,4- and2,6-hexahydrotoluene diisocyanate, toluene diisocyanate (TDI),diphenylmethane diisocyanate (MDI), pentane diisocyanate(PDI)—bio-based), and, isomers of any of these.
 32. The method accordingto claim 18, wherein the reducer is selected from the group consistingof n-butyl acetate, ethyl acetate, 2-methoxy-1-methylethyl acetate,1-methoxy-2-propyl acetate, 2-methoxy-1-propyl acetate, 2-ethoxyethylacetate, n-heptane, methylcyclohexane, toluene, acetone, VM&P naphtha,naphtha, light aliphatic solvent naphtha, acetate, isobutyl acetate,mixed xylenes, ethylbenzene, methyl ethyl ketone, dimethyl ketone,methyl n-amyl ketone, methyl isobutyl ketone, 1,2,4 trimethyl benzene,isopropylbenzene, ethyl benzene, 1-chloro-4 (triflouromethyl) benzene,propylene glycol methyl ether, and ethyl-3-ethoxy propionate andcombinations thereof.
 33. One of a coating, an adhesive, a casting, acomposite, and a sealant comprising the allophanate system madeaccording to claim
 18. 34. A method of applying the allophanate systemmade according to claim 18 to a substrate, wherein the method comprisesat least one of spraying, dipping, flow coating, rolling, brushing, andpouring.